Separation of aromatic hydrocarbons



May A5', l1942*. w. J. MA1-'rox SEPARATION OF AROMATIC HYDROCARBONS Filed April 19, 1941 bwl/21]. 7//Zaz' j M7731.

Patented May 5, 1942 UNITED STATES PATENT OFFICE william J. Matrox, chicago, nl., signor to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware Application April 19, 1941, Serial No. 389,448

9 Claims. (Cl. 26o-674) 'I'his invention relates to a process for separating ethyl benzene from 4isomeric xylenes. More specifically the process is concerned with a combination of chemical and -physical methods for separating ethyl benzene from mand pxylehes which are often present in' hydrocarbon fractions containing ethyl benzene.

Because of the very small differences between the boiling points of ethyl benzene and mand p-xylenes, separation of these aromatic hydrocarbons can not be made efficiently by means of fractional distillation. Other commercial methods of effecting such separations are either not known or have not been put into general use.

In the case of o-xylene, this isomer boils from 5 to 8 AC. (9 to 14 F.) -higher than ethyl-benzene and the other xylenes'and therefore can be substantially separated therefrom by distillation. y

Since ethyl benzene has now become a highly important compound in industrial manufacturing processes and especially in the production of styrene, the latter being used in the manufacture of resins, a suitable method is needed for separating ethyl benzene from the xylenes which either occur with it in'distillates obtained from coal tar, or are formed simultaneously in manu.- facturing processes as by the dehydrogenation and cyclization of aliphatic hydrocarbons to yield aromatic hydrocarbo In one specific embodiment the present invention comprises a process for separating ethyl benzene from a mixture comprising essentially ethyl benzene and isomeric xylenes which com'- prises fractionally distilling said mixture to re- ,moveA a relatively lower boilingfraction containof these aromatic hydrocarbons and the boiling points of the corresponding naphthenic hydrocarbons produced therefrom by hydrogenation.` Thesey different boiling points are indicated in the following table:

Ethyl benzene and alsoA some mand pxylenes are separated from the higher boiling o-xylene by fractional distillation. Since ethyl benzene boils about 8 lower than o-xylene, this ing mand p-xylenes and. ethyl benzene from a residue of higher boiling o-xylene, subjecting said relatively lower boiling fraction to catalytic hydrogenation to form a naphthenic hydrocarbon mixture including ethyl cyclohexane and dimethyl cyclohexanes, separating said naphthenic hydrocarbon mixture by distillation into dimethyl cyclohexanes and an ethyl cyclohexane fraction, catalytically dehydrogenating said ethyl cyclohexane fraction to give ethyl benzene and a hydrogen-containing gas, and recycling said` hydrogen-containing gas to further use in the hydrogenation o1'y an additional quantity of the fraction comprising essentially m and p-xylenes and ethyl benzene being charged to the lhydrogenation step of the process.

The process of this invention for separating ethyl benzene from the isomerlc xylenes makes use of the diiferences'between the boiling points separation is readily accomplished. The remaining mixture containing ethyl benzene and mand p-xylenes is then hydrogenated by any of several well-known hydrogenation processes to give a commingled mixture of ethyl cyclohexane and m'- and p-dimethyl cyclohexanes. The resulting ethyl cyclohexane, which boils from 11 to 12 C. higher than the mand p-dimethyl cyclohexanes, remains after the dimethyl cyclohexanes are removed by fractional distillation and then the ethyl cyclohexane` is dehydrogenated in the final step of the process to yield ethyl benzene. The hydrogen liberated in this dehydrogenation treatment is returned to the hydrogenation stage of the process for further use in convertingaromatic hydrocarbons into 'naphthenic hydrocarbons. As desired, the dimethyl cyclohexanes so separatedfrom ethyl cyclohexane may or may not be reconverted into xylenes by dehydrogenation.

A number of catalysts may be employed for lysts with substantially no isomerization of the products o r formation of secondary reaction products and therefore the yield lof desired naphthenichydrocarbon is practically-quantitative. A veryV emcient nickel catalyst .has been prepared by precipitating basic nickel carbonate in the presence of diatomaceous earth by adding sodium carbonate solution to al solution of 'taining about 65A o nickel and about atmospheres.

dehydrogenation.

vticularly such oxides as those yleft-hand columns oi groups V and VI of thetainin'g. a

as one of those hereinabove set iorthand-.opernickelic sulfate. The resulting precipitate vis duced with hydren 35% diacontaining tomaceous earth. Such catalysts nickel operate usually at temperatures of'from about 50 to about 200 C. and. underva pressure of 4from substantially atmospheric to 100 or more The hydrogenation stage of the present ,process may also be carried out in the process of troduced thereto are converted into the corresponding naphthenic hydrocarbons with substantially no decomposition, cracking, or other undesirable side reactions.

The products from hydrogenation reactor Il are directed therefrom through line and valve 2lto fractionator 22 of conventional design in which a hydrogen-containing gas, a 'di-methyl cyclohexane fraction, and ethyl cyclohexane are other forms of nickel such as Raney" nickel,

other supported nickel catalysts, other catalysts A containing copper, iron, cobalt, platinum, palladium, chromium, molybdenum, etc.,l as metals.l or as metal oxides either alone or in admixture with nickel or with supporting materials such as alumina, magnesiaetc. For example, an eicient hydrogenation catalyst comprises oxides of copper and chromium either with or without 'the addition of small percentages of nickel even as 1owas o.oo1 to 0.2%. catalysts or the types indicated are active for the hydrogenation of aromatic hydrocarbons when operating at temperatures `of from about 200- to about 350 C. and under a pressure cg; approximately 100 atmospheres ofvhydrogen. f.

A rather wide variety of catalysts may be used forv dehydrogenating ethyl cyclohexane to ethyl benzene-or, when desired, for converting thev di.l methyl cyclohexanes into isomeric xylenes. At temperatures varying from about 250 to'about 600' C.- andV at substantially atmospheric pressure or under a slightly elevated pressure, nickel catalysts of the types described above forhydrogenation have been found active and eiiicient for catalysts, various of' metals in the cooling and stora fio substantially-separated. The hydrogen-containing gas is directed from iractionator 22 through line 23 and valve 2l to line 38 through. which it is recycled tocommingle with thematerials charged to hydrogenation reactor I9. A substantially di- 15 methylcyclohexane fraction is withdrawn from fractionator 22` through lin'e 25 -and valve 26 to not shown, or to any other I -desired use. Asibstantially ethyl cyclohexane In` addition to these nickel metal oxides may be used, par- -periodic table and especially oxides of vanadium,

' chromium, and molybdenum, or oxidesof zinc, aluminum, magnesium, etc. used-either alone, in mixtureswith each other, or deposited -upon suit-.

able supports or carriers. 4 For the purpose of illustrating they process of the present invention, the` attached drawing shows diagrammatically one form of an apparatus in which the various steps may be carried out for separating ,ethyl benzene` from a mixture` containing ethyl benzene and isomeric xylenes. L

Referring to the drawing, a hydrocarbon 'mix.

Ature'containing ethyl benzeneV and xylenes is introduced through line I and valve 2 to pump 3 which discharges throughline I and valve l into tractionator4 6-01. conventional design in which a mixture comprising essentially ethyl benzene,- m-

and p-xylenes isseparated from relatively higher boiling',oxyl'ene, the latter material being withdrawn from fractionator. 3 through line 1, valve 3, cooler 9,:line III, and valve VII to'storage or to I which discharges` through line I3A and valve: I1

into line I2 andthehce passes through valve I3 into hydrogenation reactor Il preferably conilxed bed hydrogenation csgtalyst such ated at such a temperature and pressure that substantially all of lthe aromatic hydrocarbons infraction is directed Afrom the bottom of fractionator 22 through line 21 and valve 28 to pump 23 which discharges through line and valve 3i into dehydrogenation reactor 32 containing a catalyst suitable for converting Aethyl cyclohexane into ethyl benzene and hydrogen with substantially no cracking or decomposition into .undesired products. n

The products from dehydrogenation reactor 32 are directed through line 33 and valve `3l to gas separator 35 in which a gas comprising essentially 30 hydrogen is separated fromethyl benzene. 'The hydrogen-containinggas is withdrawn from gas separator'35 through line 36 containing valve 31. While part of the hydrogen-containing gas may be discharged through valve 31, at least a portion 35 of said gas is directed through recycle line 38 and` valve 39 .to compressorv 40 4which discharges through line 4I and valve 42 into line I2, already mentioned, through which the mixture lof aro-v matic hydrocarbons and hydrogen is introduced 40 to hydrogenation reactor I9. From gas separator 3l the ethyl benzene fraction is withdrawn through line 43, valve 4l, cooler 45,'line I6, and valve 41 to storage or to further use as desired.

According to the process of the present inven) .m tionhydrogen is used essentially as a. tool for eilecting the separation of ethyl benzene from isomeric xylenes. Since the hydrogenation and dehydrogenation reactions used in this process are accompanied by relatively low losses dueto t0 decomposition, cracking, or 'other undesirable side reactions, av highly efIicient separation of ethyl benzene is eilected. Y

-The following exampleis introduced to illustrate the results normally expected from the .55 process. although this exampleis not presented with the intention of unduly limiting the broad scope of the invention.

A hydrocarbon mixture formed by dehydro? cyclization of 100 parts -by weightl of normal octane in thel presence of a chromia-alumina catalyst and consisting of approximately 15 parts by weight of ethyl benzene, 35 parts by weight of a xylene mixture containing about equal amounts of o, m, and p-xylenes. l0 parts by weight of Ae5 octenes, and 20 parts by`weight of unconverted octane is fractionally distilled and separated-into an octane-octane fraction, a mixture comprising essentially ethyl benzene and mand p-xylenes, and a' residueconsisting of substantially pure Yo-xylene. One molecularproportion of said mixture comprising essentially ethyl benzene and mand p-xylenes is commingledv with4 molecularI proportions of vhydrogen and rthe commingled .mixture is passed at" C. under a pressure of -76 20 atmospheres through a reactor containing a aasaas xed bed ot hydrogenation catalyst comprising approximately 65% by weight of reduced nickel and'35% by weight of diatomaceo'us earth. Hydrogenation to ethyl cyclohexane and di-methyl cyclohexanes is substantially complete after one pass over the catalyst when approximately 1 volume of liquid aromatic hydrocarbon mixture is charged Der hour through 1 volume of the nickeldiatomaceous earth catalyst.

Fractional distillation of the hydrogenation product separates approximately 14 parts by weight oi substantially pure ethyl cyclohexane from a mixture containing about .24 parts by weight of di-methyl cyclohexanes and 1 part by weight of ethyl cyclohexane. Passage of the substantially pure ethyl cyclohexane fraction over a composite comprising essentially 8% by weight of chromium sesquioxide' and 92% by weight of alumina at 500 C. under substantially atmospheric pressure using an ethyl cyclohexane charging rate corresponding to a liquid space velocity of 1 gives substantially complete conversion into ethyl benzene and hydrogen, the

mand p-xylenes and a hydrogen-containing gas, and recycling said hydrogen-containing gas to further use in the hydrogenation oiv an addiand isomeric xylenes which comprises fractionally distilling said mixture to lremove a relatively lower boiling fraction containing m.- and 4p-xylenes and ethyl benzene from a residue of higher boiling o-xylene, subjecting 1 molecular proportion oi.' said relatively lower boiling fraction and at least 3 molecular proportions of lhydrogen to contact with a hydrogenating catalyst under conditions'of temperature and pressure latter being compressed and recycled to coml mingle with the mixture ot ethyl benzene, mand p-xylenes, and added hydrogen beingv conducted to the hydrogenation stage of the process. Y

The nature of the present invention and its commercial utility are evident iromthe specication and example given, although neither section is intended to unduly limit its generally broad scope.

I claimas my invention:

1. A process for separating ethyl benzene from a mixture comprising essentially ethyl benzene and isomeric xylenes which comprises fractionally distilling said mixture to remove a relatively adequate to form a naphthenic hydrocarbon mixture including ethyl cyclohexane and di-methyl cyclohexanes, separating said naphthenic hydrocarbon mixture by distillation into dimethyl cyclohexanes and an ethyl cyclohexane fraction, catalytically dehydrogenating said ethyl cyclohexane fraction to give ethyl benzene and a hydrogen-containing gas, and recycling said hydrogen-containing gas to further use in the hydrogenation of an additional quantity of the fraction comprising essentially mand p-xylenes -and ethyl benzene being charged to the hydrogenation stepof the process..

5. A process for separating ethyl benzene from .a mixture comprising essentially ethyl benzene and -isomeric xylenes which comprises tractionally distllling said mixture to remove a relatively m-xylene, and p-xylene which comprises subjecting said mixture to catalytic hydrogenation to form a naphthenic hydrocarbon mixture includcharged to the hydrogenation step of the process.

3. A process i'or separating ethyl benzene trom a mixture comprising essentially ethyl benzene, m-xylene, and p-xylene which comprises subjecting said mixture to catalytic hydrogenation to form a naphthenic hydrocarbon mixture including ethyl cyclohexane and dimethyl cyclohexanes, separating said naphthenic hydrocarbon mixture -by distillation into an ethyl cyclohexane fraction and -a dimethyl cyclohexane fraction, separately 4catalytically dehydrogenating said ethyl cyclohexane fraction and said dimethyl cyclohexane lower vboiling fraction containing mand p-xylenes and ethyl benzene from a residue of higher boiling o-xylene, subjecting 1 molecular' proportion of said relatively lower boiling traction t andvat least 3 molecular proportions of hydrogen to contact with a hydrogenating catalyst under conditions of temperature and pressure adequate to form a naphthenic hydrocarbon mixture including ethyl cyclohexane and dimethyl cyclohexanes, separating said naphthenic hydrocarbon mixture by distillation into dimethyl cyclohexanes and an ethyl cyclohexane fraction. subjecting said ethyl cyclohexane fraction to contact with a nickel-containing catalyst at a temperature 'of from about 250 to about 600.C. to form ethyl oenzene and a hydrogen-containing gas, and recycling said hydrogen-containing gas to further use in the hydrogenation of an additional duantity of the fraction comprising essentially mand p-xylenes and ethyl benzene being charged to the hydrogenation step of the process.

6. A process for separating ethyl benzene from a mixture comprising essentially ethyl benzene, m-xylene, and 'p-xylene which comprises subjecting 1 molecular proportion of said mixture and at least 3 molecular proportions of hydrogen lto contact with a dehydrogenating ,catalyst under conditions of temperature and Apressure adequate to form a naphthenic hydrocarbon mixture including ethylcyclohexane and dimethyl cyclohexanes. separating said naphthenic hydrocarbonhmixture by distillation into a dimethyl cyclohexane fraction and an ethyl cyclohexane fraction, catalytically dehydrogenating said ethyl cyclohexane fraction to give ethyl benzene and mixture being charged to the hydrogenation step of the process.

traction to giveV ethyl benzene. a mixture of 7. A process for separating ethyl benzene from a mixture lvcomprising ethyl benzene and isomeric xylenes ,which comprises .fractionally distilling said mixture to remove a relatively Y lower boiling fractioncontainingman'dp-xyl `enea and ethyl benzeneirom a residuen! high-f er boiling o'xylene,- subjecting 1 molecular'proportion of said relatively lower boiling fraction and atleast 3 molecular proportions of hydrogen' to contact' with a hydrogenating catalystunder conditions of temperature and pressure adequate to form anaphthenic-hydroc'arbon mixture inv cluding' ethyl cyclohexaneand dimethyl cyclohexanes, separating said naphthenic Ihydrocarbon mixture by distillation into; dimethyl cyclo` hexanes and an ethyllcyclohexane fractiomsuh- `subjecting said ethyl cyclohexane traction 'to contact with a compositeof a maior proportion ot a carrier and a relatively smaller proportion o! an oxidevof an! element selected from the members of the left-hand column of group VI 'oz the periodic table to form ethyl benzene and jecting said ethylcyclohexane fraction to contact with `a composite of a major proportion of a carrier and a relatively smaller proportion of an oxide-oi. an: element selected' from the members of theleft-hand column of groupl Vo! the periodic table to form ethyl benzene and a hydrogen-containing Bas. 'and recycling said hy-A drogen-containing .gas to further use in the hydrogenationci an additional quantity o!I said relatively lower boiling traction containing nti-v and p-xylenes and ethyl benzene being charged to the hydrogenation stepof. the process.

' 8. Aprocess lor separating ethyl benzene from a mixture comprising essentiallyv ethyl benzene and isomeric xylenes which comprises fractionally distilling said mixture to removev a relatively lower boiling fraction containing mand p-xylenes and lethyl .benzene from a residue of higher boiling oxy1ene, subjecting 1 molecular proportion of said relatively lower boiling -irac' a hydrogen-containing gas, and recycling said hydrogen-containing gas to `further" use in the 'hydrogenation of an additional quantity of said relatively lower boiling traction containingm- 'contactfwith a hydrogexating catalyst under conditions of temperature and pressure adequate to form a naphthenic hydrocarbon mixturefin cyclohexane fraction and a dimethyl cyclohextion and lat least 3 molecular proPOrtions of hydrogen to contact with a hydrogenating catalyst under conditions of temperature and pressure adequate to form naphthenic hydrocarbon mixture including eth l cyclohexanepand. dimethyl cyclohexanes, separating said naphthenic hydrocarbon mixture by distillation into dimethyl cyclohexanes and an ethyl cyclohexane fraction.

cluding ethyl cyclohexane andy mand iJ-dimethyl ,cyclohexanea separating said naphtl'lenlcl hydrocarbon mixture by distillation into an ethyl ane fraction, 'lleparatelyil catalytically dehydrogenating said ethyl cyclohexane fraction and said dimethyl cyclohexane traction in the presence of a composite oi' a maior proportion of alumina and a relatively smaller proportion'of an oxide of chromium to give ethyl benzene, a mixture ot m-xylene and p-xylene, and a hydrogen-contaming gas, and recycling said hydl'cgcn-containing ygals to further use in the hydrogenation o! an additional quantity o! Vsaid relatively lower boiling Afraction containing m- -and p-xylenes and ethyl benzene being chargedy to the hydrogenation step'ot the process. v

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